Process for reacting a mercaptobenzo-thiazole with a carboxylic acid halide



Patented Aug. 6 1935 2,010,000 7 PROCESS 'FOR REACTING A MERCAPTO-BENZO-THIAZOLE WITH ACID HALIDE- A CARBOXYLIC Marion Harman, Nitr'o, W;Va., assi nor to The Rubber Service Laboratories Company,

Akron, Ohio, a corporation of Ohio Nb Drawing; Original application July1, 1931, Serial N0. 548,255. Divided and this'application May 61933,5erial No. 669,791

"1 Claims. (01. 200-44) The present invention relates to the manufactureof "a new class of compounds comprising reaction products o famercapto-aryl-thiazole and lanforganicacidhalide" The "new" class ofcom- 5' pounds possesses'valuable accelerating properties when employedin the process of vulcanizing rubber. v V

j Compounds of the preferred class may in gen- 1eralbe prepared bytreating a mercapto-aryl- .Lthiazole or an, inorganic or organic saltthereof with" an organic acid. halide under reaction conditionsiwithconsequent elimination of the corresponding hydroh'alogenicacid or salt thereof.

Example I Morespecifically one of l the preferred new class ofcompounds, for example, a reaction prod! uct, of mercaptobenzo'thiazole" and phthalyl chloride, was, prepared as follows:Substantially two molecular proportions .of "merca'ptoebenzo thiazoleand substantially two molecular propor 'tio'nsof, s'odiumhydroxide, thelatter being dissolved in avery small'ar'n'ountoi water, were agitatedwith a convenient quantity of a suitable solvent, for example, acetone,until solution took place. Substantially one molecular proportion of'phthalylchloride was thenadded slowlyv thereto while maintaining atemperaturenot higher than approximately-10} C. The resulting mixturewas preferably agitatedfor, a suitable period, prefer.- ablyapproximately; thirty minutes,-. after all the phthalyl chloridehad beenadded. The-reaction product was filtered OE and washed with asuitablesolvent, for exampleacetone, to rer'noveany unreactedmercapto-benzo thiazole, and further washed with water. The productobtained wasa fine, pale yellowpowderp Itis believed theprodnot so'obtained may be represented by the following formula. v

The above described materialfhas also been prepared by the followingmethod: Substantially two molecular'proportions of the salt formed byreacting mercapto-benzo thiazole with diphenyl-j guanidine was suspendedin a convenient quantity of water and the mixture rapidly agitated. Asolution of substantially one molecular proportion of phthaiyl chloridein a small quantity of a volatile solvent immiscible in water, forexample carbon tetrachloride, benzol and the like, was added slowlythereto, and after further agitation the product formed was filteredoff, washed with ater and dried. A finely divided crystalline productwas obtained.

v The product described above was also prepared by the following method:Substantially one molecular proportion of phthalyl chloride 'dis+ solvedin a small quantity of a volatile solvent im misciblein water, forexample, benzol, was added slowiyto a rapidly agitated solutionofsubstantially two molecular proportions of the sodium salt ofmercapto-benzo-thiazole in water, maintained within the temperaturerange of approximately 6 to 25 C., but preferably at approxi mately 10to C. It is believed that the v05 latilization of thesolvent immisciblein water, as employed in the above process, aids in producing a veryfinely dividedproduct. After further agitation analkaline material, forexample, sodium carbonate, was preferablyadded to dissolve any unreactedmercapto-benzo-thiazole, and,

after further agitation, the product formed was filtered off, washedfree of alkali, and dried. The

product obtained was a fine, pale yellow powder, melting atapproximately 127 to 129 C. I

A reaction product'of mercapto-benzo-thiazole and phthalyl chloride wasalso prepared by heating substantiallytwo molecular proportions-of Imercapto-benzo-thiazole and substantially 1 ne molecular proportion ofphthalyl chloride in-the absence of asolvent at approximately to untilthe reaction was completed.

Example II tion of the sodium salt of mercapto-benzo-thiazole, whilerapidly agitating the latter taining at a temperature range ofapproximately 6 to 25 C., but preferably at approximately 3.0 to 15 C.After further agitation the product foried was extracted with analkaline material, for example, sodium carbonate, further washed withwater, and dried. It is believed the product so obtained may berepresented by the following formula A reaction product ofmercapto-benzo--thiazole and benzoyl chloride was also prepared bysuspending substantially one molecular proportion of thediphenyl-guanidine salt of mercapto-benzo thiazole in water, stirringrapidly at approximately 20 to 25 C., and adding slowly theretosubstantially one molecular proportion of benzoyl chloride dissolved ina small quantity of a volatile solvent immiscible in water, for example,ben- Z01. The product formed was washed with water, further washed withan alkaline solution, for example, a sodium carbonate solution, andagain washed with water.

A reaction product of mercapto-benzo-thiazole and benzoyl chloride wasalso prepared by refluxing substantially equal molecular proportions ofmercapt-benzo-thiazole and benzoyl chloride in a high-boiling solvent,for example, orthodichlorbenzene. The product was isolated by remc-v thesolvent employed by any convenient me as for example, by steamdistillation. r dual product obtained was a brown resinou. so

A reaction product of mercapto-benzo-th1azole and benzoyl chloride wasalso prepared by heating in the absence of a solvent a mixture ofsubstantially equal molecular proportions of mercapto-benzo-thiazole andbenzoyl chloride slowly to approximately 180, and maintaining at thistemperature until reaction was completed.

Example 111 Another compound of the preferred class, for example, areaction product of mercapto-benzothiazole and para-nitro-benzoylchloride, was prepared as follows: Substantially eeui-molecularproportions of mercapto-benzo-thiazole and sodium hydroxide weredissolved in a suitable solvent, for example, a mixture of acetone and asmall quantity of water. To this solution sub stantially one molecularproportion of para-nitro-benzoyl chloride dissolved in a small quantityof a suitable solvent, for example. acetone, added slowly at atemperature of approxi ately 5 to 10 C. The mixture was stirred for a"rt time, and the product formed filtered off, washed with a suitablesolvent, for example, acetone, to remove anyfree-mercapto-benzo-thiazole, and further washed with water. Thereaction product consisted of a yellow powder, melting at approximately210 to 217 C. It is believed the product so obtained may be representedby the following formula Example IV.

A further example of. the preferred class of compounds was prepared byreacting mercapto-benzothiazole 'v h ethyl ohloro=sulfonate possessingthe formula CeilsOSGzCl. The method was follows: Substantially onemolecular prop rtion of ethyl chlorosulfonate was added to substantiallyone molecular proportion of meroapto-- benzo-thiazole in the presence ofa suitable liquid medium, for example, chloroform. After standing for aperiod of time, preferably for several hours, an oil separated. Asuitable solvent, for example, naphtha, was then preferably added to thesolution to more completely effect the precipitation of the oil. Thesaid oil was drawn oil, and could then be washed with a suitablesolvent, for example, naphtha. The product thus purified was dried,preferably in vacuo at approximately 80 C. It cons'sted of a brown oil.It is believed the material prepared as described has the followingformula N ornfiosorso The invention described is not limited to theexact temperatures, proportions and the like hereinbefore set forth butis limited solely by the claims attached hereto as part of thisspecification.

This case is a division of a co-pending application Serial No. 548,255,filed July 1, 1931 by the present applicant.

What is claimed is:

1. A process for the manufacture of a benzothiazyl ester, whichcomprises adding a solution of a carboxylic acid halide of the benzeneseries in a small quantity of an inert volatile solvent immiscible inwater slowly to water containing a diaryl substituted guanidine salt ofa mercapto benzo-thiazole, aryl substituents consisting in members ofthe benzene series only, while agitating the latter. I

A process for the manufacture of a memothiazyl ester, which comprisesadding a solution of a carboxylic acid chloride of the benzene series ina small quantity of an inert volatile solvent immiscible in water slowlyto water containing a diaryl substituted guanidine salt of amercaptobenzo-thiazole, said aryl substituents consisting in members ofthe benzene series only, while agitating the latter.

3. A process for the manufacture of a homo- 'hiazyl ester, whichcomprises adding a solution of a carboxylic acid halide of the benzeneseries in a small quantity of an inert volatile solvent immiscible inwater slowly to water containing a diphenyl guanidine salt of amercapto-benzothiazole, while agitating the latter.

l. A process for the manufacture of a benzothiazyl ester, whichcomprises adding a solution of benzoyl chloride in a small quantity ofan inert volatile solvent immiscible in water slowly to water containinga diphenyl guanidine salt of mercapto-benzo-thiazole, while agitatingthe latter.

5. A process for the manufacture of a benzothiazyl estenwhich comprisesadding a solution of substantially one molecular proportion of benzoylchloride in a small quantity of, an inert volatile solvent immiscible inwater slowly to water containing substantially one molecular proportionof the diphenyl guanidine salt of mercaptobenzo-thiazole, whileagitating the latter.

6. A process for the manufacture of a benzothiazyl ester, whichcomprises adding a solution of substantially one molecular proportion ofbenzoyl chloride in a small quantity of benzol slowly to watercontaining the diphenyl guanidine salt of mercapto-benzo-thiazole, whileagitating the latter.

7. A process for the manufacture of a benzothiazyl ester, whichcomprises adding a solution of substantially one molecular proportion ofbenzoyl chloride in a small quantity of benzol slowly to watercontaining the diphenyl guanidine salt of mercapto-benzo-thiazole, whileagitating and maintaining the latter at a temperature betweensubstantially 20 to 25 C.

MARION W. HARMAN.

